CN102504272A - Modified lignosulfonate water reducing agent and preparation method thereof - Google Patents
Modified lignosulfonate water reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified lignosulfonate water reducing agent and a preparation method thereof. The preparation method of the modified lignosulfonate water reducing agent comprises the following steps: oxidizing lignosulfonate under the action of an oxidant, and subjecting the oxidized lignosulfonate to graft polymerization with acrylic acid, maleic anhydride and polyethylene glycol to obtain the modified lignosulfonate water reducing agent. Compared with the prior art, because a large number of polar groups are introduced into lignosulfonate molecules, and the grafted polyethylene glycol is in a branched-chain structure, the side chains of the lignosulfonate increase to form a branch structure, and the water reducing effect is enhanced. The experiment proves that the prepared modified lignosulfonate water reducing agent has a high water reducing rate of about 22-26%. In addition, because the adopted lignosulfonate and modified monomers have low cost, the cost of the prepared modified lignosulfonate water reducing agent is reduced.
Description
Technical field
The present invention relates to the water reducer technical field, more particularly, relate to a kind of modified lignin mahogany sulfonate water reducer and preparation method thereof.
Background technology
In the last thirty years, concrete has obtained developing rapidly and has used widely in China, and some large size cities and coastland have very high popularity rate especially at home, make the research of concrete admixture obtain concern more and more widely.Water reducer is the concrete admixture of using always; Be aniorfic surfactant; On the one hand; Water reducer is adsorbable to make particle show electrical property in cement particle surface, thereby makes between cement granules because band identical charges and repelling each other, so cement granules is disperseed and release particles between redundant moisture; On the other hand, the adding of water reducer makes cement particle surface form adsorption film, influences the hydration rate of cement; Make the growth of cement stone crystalline more perfect; Reduce the capillary gap of moisture evaporation, network structure is more fine and close, thereby has improved the hardness and the compact structure property of sand-cement slurry.
Present widely used water reducer comprises sulfonated lignin water reducer, naphthalene water reducer, melamine system water reducer, thionamic acid based water reducer, aliphatic water reducing agent and poly carboxylic acid series water reducer etc.Wherein, The sulfonated lignin water reducer is the sub product that sulphite process is produced paper pulp; Have with low costly, raw material sources are characteristics widely, and can increase concrete intensity; Generally by the preparation of following method: with timber and the S-WAT lignosulfonic acid bisulfate waste liquor that boiling obtains under HTHP ferment successively desugar, extract alcohol, concentrated and spraying drying; Promptly get brown powdered sulfonated lignin, its relative molecular mass is 2000～100000, and often with carbohydrate and other reducing substance.The sulfonated lignin water reducer was used to the concrete from early 1930s, and water-reducing rate belongs to the coventional type cement water reducing agent between 8～9%, was applicable to various cast-in-place and ready-formed concrete workses.
In order further to improve the water-reducing rate of sulfonated lignin water reducer, satisfy the requirement of high performance concrete, the correlative study personnel have carried out modification to these sulfonated lignin.For example; Publication number is the preparation method that the one Chinese patent application of CN101648979A openly provides a kind of lignosulfonate series air entraining and water reducing admixture for concrete; This method is specially: sulfonated lignin are dissolved in the water with weight, add catalyzer, oxygenant, amine and aldehydes, obtain reaction product behind the amination reaction; The mixture of useful as concrete, water-reducing rate about 18.1%.In addition; Publication number is the preparation method that the one Chinese patent application of CN101885810A discloses a kind of amide modified lignosulfonate high-efficiency water reducing agent; This method is passed through the oxygenant oxidation with sulfonated lignin under the condition of acidity and catalyzer existence, under alkaline condition and radical initiator initiation, react with acrylamide graft then.
The inventor considers, other a kind of modified lignin mahogany sulfonate water reducer and preparation method thereof is provided, and the modified lignin mahogany sulfonate water reducer water-reducing rate of this method preparation is higher, and has reduced cost.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of modified lignin mahogany sulfonate water reducer and preparation method thereof, and the water-reducing rate of the water reducer of this method preparation is higher, and has reduced cost.
In order to solve above technical problem, the present invention provides a kind of preparation method of modified lignin mahogany sulfonate water reducer, may further comprise the steps:
Sulfonated lignin and oxygenant are mixed in solvent, obtain first reaction product after the reaction;
Said first reaction product, catalyzer and vinylformic acid are mixed, obtain second reaction product after the reaction;
Said second reaction product, initiator and maleic anhydride are mixed, obtain the 3rd reaction product after the reaction;
Said the 3rd reaction product is mixed with polyoxyethylene glycol, obtain the modified lignin mahogany sulfonate water reducer after the reaction.
Preferably, said sulfonated lignin are calcium lignin sulphonate, sodium lignosulfonate or magnesium lignosulfonate.
Preferably, said oxygenant is one or more in potassium permanganate, hydrogen peroxide and the ammonium persulphate.
Preferably, said catalyzer be ferrous sulfate, S-WAT, sodium sulfite anhy 96 and Sodium Pyrosulfite one or more.
Preferably, said initiator is azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline salt hydrochlorates.
Preferably, the weight ratio of said sulfonated lignin, oxygenant, solvent, catalyzer, vinylformic acid, initiator, maleic anhydride and polyoxyethylene glycol is 100: (1～5): (100～300): (1～15): (10～30): (10～20): (50～90): (30～60).
Preferably, the said temperature of reaction that obtains second reaction product is 75～90 ℃, and the reaction times is 1～8h.
Preferably, the said temperature of reaction that obtains the 3rd reaction product is 70～90 ℃, and the reaction times is 0.5～5h.
Preferably, the said temperature of reaction that obtains the modified lignin mahogany sulfonate water reducer is 70～90 ℃, and the reaction times is 1～5h.
The modified lignin mahogany sulfonate water reducer of above-mentioned preparing method's preparation.
The invention provides a kind of modified lignin mahogany sulfonate water reducer and preparation method thereof; This method comprises: with sulfonated lignin oxidation under the oxygenant effect; Then under catalyzer and initiator effect; With vinylformic acid, maleic anhydride and polyoxyethylene glycol generation graft polymerization reaction, obtain the modified lignin mahogany sulfonate water reducer.Compared with prior art, the present invention has introduced a large amount of polar groups in the lignosulfonic acid molecules of salt, simultaneously, because the grafted polyoxyethylene glycol has branched structure, thereby the side chain of sulfonated lignin is increased, and forms branched structure, has strengthened water-reducing effect.Experimental result shows that the water-reducing rate of the sulfonated lignin water reducer of the present invention's preparation is higher, about 22%～26%.In addition; Because sulfonated lignin and the equal wide material sources of modified monomer that the present invention adopts; Cheap, thus the cost of the modified lignin mahogany sulfonate water reducer of preparation reduced, make this modified lignin mahogany sulfonate water reducer have more wide application in the high efficiency water reducing agent field.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of preparation method of modified lignin mahogany sulfonate water reducer, may further comprise the steps:
Sulfonated lignin and oxygenant are mixed in solvent, obtain first reaction product after the reaction;
Said first reaction product, catalyzer and vinylformic acid are mixed, obtain second reaction product after the reaction;
Said second reaction product, initiator and maleic anhydride are mixed, obtain the 3rd reaction product after the reaction;
Said the 3rd reaction product is mixed with polyoxyethylene glycol, obtain the modified lignin mahogany sulfonate water reducer after the reaction.
In above-mentioned preparation process, the present invention under catalyzer and initiator effect, with vinylformic acid, maleic anhydride and polyoxyethylene glycol generation graft polymerization reaction, obtains the modified lignin mahogany sulfonate water reducer then with sulfonated lignin oxidation under the oxygenant effect.
The present invention is the feedstock production water reducer with sulfonated lignin; These sulfonated lignin are claimed sulfonated lignin again, are the sub products of sulphite process papermaking wood pulp, are linear polymer; Have with low cost; Raw material sources are characteristics widely, and can increase concrete intensity, practice thrift cement.Further; Because sulfonated lignin are the product of chemical pulping, the radical on its phenyl ring is more, has stronger reactive behavior; On the phenyl ring He on the side chain all the functionalization chemical reaction can take place; Therefore, the present invention has some specific physical and chemical performance in order to make Sulfite lignin, and Sulfite lignin are carried out chemical modification.The sulfonated lignin that the present invention adopts can adopt commercial product, are preferably calcium lignin sulphonate, sodium lignosulfonate or magnesium lignosulfonate.
The oxygenant that the present invention adopts is preferably one or more in potassium permanganate, hydrogen peroxide and the ammonium persulphate; Said solvent is preferably water.Said with sulfonated lignin and oxygenant in solvent in the blended step, said hybrid mode preferably adopts stirring method, more preferably stirs 5～20 minutes, more preferably stirs 10 minutes.In the step that obtains first reaction product, oxygenant makes the sulfonated lignin molecular rupture, produce to have the highly active radical end of the chain, and reaction generates the molecule long-chain under the oxygenant effect, thus the growth of sulfonated lignin molecular chain; Simultaneously, the methoxyl group in the part sulfonated lignin molecular chain changes phenolic hydroxyl group under the oxygenant effect; Further, under the oxygenant effect, part phenolic hydroxyl group and alcoholic extract hydroxyl group continue reaction and generate carboxyl, finally prepare first reaction product.
After obtaining first reaction product, said first reaction product, catalyzer and vinylformic acid are mixed, obtain second reaction product after the reaction.Said catalyzer be preferably ferrous sulfate, S-WAT, sodium sulfite anhy 96 and Sodium Pyrosulfite one or more.The said temperature of reaction that obtains second reaction product is preferably 75～90 ℃, and more preferably 80～85 ℃, more preferably 85 ℃; The said reaction times is preferably 1～8h, more preferably 2～5h, more preferably 3h.
In addition, the initiator of the present invention's employing is preferably azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline salt hydrochlorates.The said temperature of reaction that obtains the 3rd reaction product is preferably 70～90 ℃, and more preferably 75～85 ℃, more preferably 80 ℃; The said reaction times is preferably 0.5～5h, more preferably 1～3h, more preferably 1h.The temperature of reaction that obtains the modified lignin mahogany sulfonate water reducer according to the invention is preferably 70～90 ℃, and more preferably 75～85 ℃, more preferably 80 ℃; The said reaction times is preferably 1～5h, more preferably 1～3h, more preferably 2h.In above-mentioned preparation process, reaction is all preferably carried out under agitation condition, and this whipping process can make each material thorough mixing, is beneficial to the formation of modified lignin mahogany sulfonate water reducer.
In above-mentioned preparation process; Under the oxygenant existence condition, the ether in the sulfonated lignin macromole, alcoholic extract hydroxyl group and phenolic hydroxyl group etc. are oxidized to living radical, then under catalyzer and action of evocating; With vinylformic acid, maleic anhydride and part polyoxyethylene glycol generation graft polymerization reaction; Form the block macromolecular chain, thereby in the lignosulfonic acid molecules of salt, introduced a large amount of polar groups, grafting simultaneously have a branched structure monomer be that polyoxyethylene glycol makes side chain increase; Form branched structure, strengthened the dispersion water-reducing effect of water reducer.
The raw material that the present invention adopts preferably adopts following weight ratio; Thereby prepare the modified lignin mahogany sulfonate water reducer; Promptly; The weight ratio of said sulfonated lignin, oxygenant, solvent, catalyzer, vinylformic acid, initiator, maleic anhydride and polyoxyethylene glycol is preferably 100: (1～5): (100～300): (1～15): (10～30): (10～20): (50～90): (30～60), more preferably 100: (3～5): (200～300): (10～15): (20～30): (15～20): (70～90): (45～60).
Among the preparation method provided by the invention; The interpolation of each raw material has great importance in proper order, promptly in above-mentioned interpolation in proper order down, has realized in the lignosulfonic acid molecules of salt, introducing a large amount of polar groups; Grafting simultaneously has the polyoxyethylene glycol of branched structure; Thereby the side chain of sulfonated lignin is increased, form branched structure, strengthened water-reducing effect.
Compared with prior art; The invention provides the preparation method of other a kind of sulfonated lignin water reducer; This method is with the oxidation of sulfonated lignin through oxygenant; With reactions such as vinylformic acid, maleic anhydride and polyoxyethylene glycol, realize chemical modification, thereby obtained a kind of modified lignosulfonate high-efficiency water reducing agent then sulfonated lignin.The present invention has more polar group and has the group than severely sterically resistance effect through having introduced; And in sulfonated lignin grafting have a polyalkylene glycol monomer of linear chain structure; Change the molecular structure and the molecular weight size of sulfonated lignin, improved the diminishing dispersion effect and the retarding effect of sulfonated lignin; Secondly, the equal price of modified monomer that the present invention adopts is cheap, thereby has reduced the cost of the modified lignin mahogany sulfonate water reducer of preparation; Once more, this preparing method's technology is simple, has improved the modified condition of harshness of the prior art, makes the modified lignin mahogany sulfonate water reducer of preparation obtain more wide development in the high efficiency water reducing agent field.
Accordingly, the present invention also provides a kind of modified lignin mahogany sulfonate water reducer of above-mentioned preparing method's preparation.When this modified lignin mahogany sulfonate water reducer used, said modified lignosulfonate high-efficiency water reducing agent volume was preferably 0.25%～0.5% of cement quality, and more preferably 0.4%～0.5%.Compared with prior art; The water-reducing rate of the modified lignin mahogany sulfonate water reducer of the present invention's preparation is higher; When having big workability, can not influence quality of concrete, be a kind of high efficiency water reducing agent that is applied in the concrete works; And progressively become effective substitute of naphthalene series high-efficiency water-reducing agent, have vast potential for future development and realistic meaning.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The chemical reagent that adopts in the embodiment of the invention is commercial.
Embodiment 1
In reactor drum, add 100 parts of calcium lignin sulphonates, 100 parts of water and 1 part of potassium permanganate, stir 10min; In said reactor drum, add 5 parts of ferrous sulfate and 10 parts of vinylformic acid, 85 ℃ are reacted 3h down; Then, in said reactor drum, add 10 parts of azo-bis-isobutyrate hydrochlorides and 50 parts of maleic anhydrides, 80 ℃ are reacted 1h down; In said reactor drum, slowly add 30 parts of polyoxyethylene glycol, 80 ℃ are reacted 2h down; Reaction is cooled to the sulfonated lignin water reducer that room temperature promptly makes modification after accomplishing.
Embodiment 2
In reactor drum, add 100 parts of calcium lignin sulphonates, 200 parts of water and 3 parts of potassium permanganate, stir 10min; In said reactor drum, add 10 parts of ferrous sulfate and 20 parts of vinylformic acid, 85 ℃ are reacted 3h down; Then, in said reactor drum, add 15 parts of azo-bis-isobutyrate hydrochlorides and 70 parts of maleic anhydrides, 80 ℃ are reacted 1h down; In reactor drum, slowly add 45 parts of polyoxyethylene glycol, 80 ℃ are reacted 2h down; Reaction is cooled to room temperature after accomplishing, and promptly makes the sulfonated lignin water reducer of modification.
Embodiment 3
In reactor drum, add 100 parts of calcium lignin sulphonates, 300 parts of water and 5 parts of potassium permanganate, stir 10min; In said reactor drum, add 15 parts of sodium sulfite anhy 96s and 30 parts of vinylformic acid, 85 ℃ are reacted 3h down; In said reactor drum, add 20 parts of azo two isobutyl imidazoline salt hydrochlorates and 90 parts of maleic anhydrides, 80 ℃ are reacted 1h down; In reactor drum, slowly add 60 parts of polyoxyethylene glycol, 80 ℃ are reacted 2h down; Reaction is cooled to room temperature after accomplishing, and promptly makes the sulfonated lignin water reducer of modification.
The modified lignin mahogany sulfonate water reducer that respectively embodiment of the invention 1～3 is prepared, commercially available commercially available naphthalene water reducer and the correlated performance of unmodified unmodified calcium lignin sulphonate are measured.Wherein, the present invention does not all have special restriction for the manufacturer of said commercially available commercially available naphthalene water reducer and unmodified unmodified calcium lignin sulphonate and model etc., is product well known to those skilled in the art and model.The process of being specially is: adopt reference cement; Measure the performances such as flowing degree of net paste of cement of the modified lignosulfonate high-efficiency water reducing agent of embodiment 1～3 preparation, unmodified sulfonated lignin water reducer and commercially available commercially available naphthalene water reducer according to GB/T 8077-2000-; Wc is 0.29; The water reducer volume is 0.45% (solid content) of cement quality, and the result is as shown in table 1.
The water reducer of table 1 embodiment of the invention preparation and the performance of commercially available water reducer
Can know that from table 1 unmodified sulfonated lignin are used for cement paste as water reducer, it is all relatively poor to starch degree of mobilization, water-reducing rate, time of coagulation, ultimate compression strength only; The kind modified lignin mahogany sulfonate that uses embodiment 1～3 preparation in the cement paste experiment respectively is during as water reducer; Clean slurry degree of mobilization, water-reducing rate and ultimate compression strength etc. all meet or exceed naphthalene series high-efficiency water-reducing agent; Experimental result shows; The water-reducing rate of the sulfonated lignin water reducer of the present invention's preparation is higher, and about 22%～26%.
And; The cement adaptability of the modified lignin mahogany sulfonate water reducer of the present invention's preparation is good, and usage range is wide, and is with low cost; Utilized the sub product in the paper mill sludge simultaneously; Have inexpensive characteristics of high efficiency, economic benefit and social benefit are better, should be widely promoted in the today of developing a circular economy with low-carbon economy.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a modified lignin mahogany sulfonate water reducer may further comprise the steps:
Sulfonated lignin and oxygenant are mixed in solvent, obtain first reaction product after the reaction;
Said first reaction product, catalyzer and vinylformic acid are mixed, obtain second reaction product after the reaction;
Said second reaction product, initiator and maleic anhydride are mixed, obtain the 3rd reaction product after the reaction;
Said the 3rd reaction product is mixed with polyoxyethylene glycol, obtain the modified lignin mahogany sulfonate water reducer after the reaction.
2. preparation method according to claim 1 is characterized in that, said sulfonated lignin are calcium lignin sulphonate, sodium lignosulfonate or magnesium lignosulfonate.
3. preparation method according to claim 1 is characterized in that, said oxygenant is one or more in potassium permanganate, hydrogen peroxide and the ammonium persulphate.
4. preparation method according to claim 1 is characterized in that, said catalyzer be ferrous sulfate, S-WAT, sodium sulfite anhy 96 and Sodium Pyrosulfite one or more.
5. preparation method according to claim 1 is characterized in that, said initiator is azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline salt hydrochlorates.
6. preparation method according to claim 1; It is characterized in that the weight ratio of said sulfonated lignin, oxygenant, solvent, catalyzer, vinylformic acid, initiator, maleic anhydride and polyoxyethylene glycol is 100: (1～5): (100～300): (1～15): (10～30): (10～20): (50～90): (30～60).
7. preparation method according to claim 1 is characterized in that, the said temperature of reaction that obtains second reaction product is 75～90 ℃, and the reaction times is 1～8h.
8. preparation method according to claim 1 is characterized in that, the said temperature of reaction that obtains the 3rd reaction product is 70～90 ℃, and the reaction times is 0.5～5h.
9. preparation method according to claim 1 is characterized in that, the said temperature of reaction that obtains the modified lignin mahogany sulfonate water reducer is 70～90 ℃, and the reaction times is 1～5h.
10. the modified lignin mahogany sulfonate water reducer of any preparation method preparation of claim 1～9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610514A (en) * | 2014-12-30 | 2015-05-13 | 福建清源科技有限公司 | Modified lignosulfonate water-reducing agent and preparation method thereof |
| CN107722198A (en) * | 2017-09-22 | 2018-02-23 | 安徽省阜南绿原化工有限公司 | A kind of preparation method of sulfonated starch polycarboxylic acids lignin copoly type water reducer |
| CN108298922A (en) * | 2018-05-06 | 2018-07-20 | 段宝荣 | A kind of building high strength grout and preparation method thereof |
| CN109928659A (en) * | 2019-04-04 | 2019-06-25 | 南京瑞固聚合物有限公司 | The water-reducing agent and preparation method thereof of high water reduction type |
| CN110437468A (en) * | 2019-07-31 | 2019-11-12 | 中国林业科学研究院林产化学工业研究所 | The response type surfactant active prepared by lignosulfonates and alkenyl succinic anhydride |
| CN113321440A (en) * | 2021-07-06 | 2021-08-31 | 四川宇砼建材有限公司 | Modified lignosulfonate water reducing agent and preparation method thereof |
| CN113773455A (en) * | 2021-09-22 | 2021-12-10 | 武汉纺织大学 | Photochromic sodium lignin sulfonate and preparation method and application thereof |
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| CN101885810A (en) * | 2010-07-12 | 2010-11-17 | 西南科技大学 | Method for preparing amide modified lignosulfonate high-efficiency water reducing agent |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885810A (en) * | 2010-07-12 | 2010-11-17 | 西南科技大学 | Method for preparing amide modified lignosulfonate high-efficiency water reducing agent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610514A (en) * | 2014-12-30 | 2015-05-13 | 福建清源科技有限公司 | Modified lignosulfonate water-reducing agent and preparation method thereof |
| CN104610514B (en) * | 2014-12-30 | 2017-08-29 | 福建清源科技有限公司 | A kind of modified lignosulfonate water reducing agent and preparation method thereof |
| CN107722198A (en) * | 2017-09-22 | 2018-02-23 | 安徽省阜南绿原化工有限公司 | A kind of preparation method of sulfonated starch polycarboxylic acids lignin copoly type water reducer |
| CN108298922A (en) * | 2018-05-06 | 2018-07-20 | 段宝荣 | A kind of building high strength grout and preparation method thereof |
| CN109928659A (en) * | 2019-04-04 | 2019-06-25 | 南京瑞固聚合物有限公司 | The water-reducing agent and preparation method thereof of high water reduction type |
| CN110437468A (en) * | 2019-07-31 | 2019-11-12 | 中国林业科学研究院林产化学工业研究所 | The response type surfactant active prepared by lignosulfonates and alkenyl succinic anhydride |
| CN113321440A (en) * | 2021-07-06 | 2021-08-31 | 四川宇砼建材有限公司 | Modified lignosulfonate water reducing agent and preparation method thereof |
| CN113773455A (en) * | 2021-09-22 | 2021-12-10 | 武汉纺织大学 | Photochromic sodium lignin sulfonate and preparation method and application thereof |
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Effective date of registration: 20190320 Address after: Room 208, No. 1 Building, No. 9 Wanjiang Avenue, Jiangbei Industrial Concentration Area, Wuhu City, Anhui Province Patentee after: Anhui Conch New Materials Technology Co.,Ltd. Address before: 276034 Renmin Street, Hedong District, Linyi City, Shandong Province, 369 Patentee before: SHANDONG HONGYI TECHNOLOGY Co.,Ltd. |
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| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 241000 room 208, building 1, No.9, Wanjiang Avenue, Jiangbei industrial concentration area, Jiujiang District, Wuhu City, Anhui Province Patentee after: Anhui Conch Material Technology Co.,Ltd. Address before: Room 208, No. 1 Building, No. 9 Wanjiang Avenue, Jiangbei Industrial Concentration Area, Wuhu City, Anhui Province Patentee before: Anhui Conch New Materials Technology Co.,Ltd. |